Continuous three dimensional fabrication from immiscible liquids

ABSTRACT

A method of forming a three-dimensional object is carried out by: providing a carrier and a pool of immiscible liquid, the pool having a liquid build surface, the carrier and the liquid build surface defining a build region therebetween; filling the build region with a polymerizable liquid, wherein the immiscible liquid is immiscible with the polymerizable liquid (in some embodiments wherein the immiscible liquid has a density greater than the polymerizable liquid); irradiating the build region through at least a portion of the pool of immiscible liquid to form a solid polymer from the polymerizable liquid and advancing the carrier away from the liquid build surface to form the three-dimensional object comprised of the solid polymer from the polymerizable liquid. Optionally, but in some embodiments preferably, the method is carried out while also continuously maintaining a gradient of polymerization zone between the liquid build surface and the solid polymer and in contact with each thereof, the gradient of polymerization zone comprising the polymerizable liquid in partially cured form.

RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.15/302,843, which is a national stage of PCT/US2015/026613, filed Apr.20, 2015, which claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/984,099, filed Apr. 25, 2014, the disclosures ofwhich are incorporated by reference herein in their entireties.

FIELD OF THE INVENTION

The present invention concerns methods and apparatus for the fabricationof solid three-dimensional objects in a bottom-up fashion from animmiscible liquid layer or pool.

BACKGROUND OF THE INVENTION

In conventional additive or three-dimensional fabrication techniques,construction of a three-dimensional object is performed in a step-wiseor layer-by-layer manner. In particular, layer formation is performedthrough solidification of photo curable resin under the action ofvisible or UV light irradiation. Two techniques are known: one in whichnew layers are formed at the top surface of the growing object; theother in which new layers are formed at the bottom surface of thegrowing object.

If new layers are formed at the top surface of the growing object, thenafter each irradiation step the object under construction is loweredinto the resin “pool,” a new layer of resin is coated on top, and a newirradiation step takes place. An early example of such a technique isgiven in Hull, U.S. Pat. No. 5,236,637, at FIG. 3. A disadvantage ofsuch “top down” techniques is the need to submerge the growing object ina (potentially deep) pool of liquid resin and reconstitute a preciseoverlayer of liquid resin.

If new layers are formed at the bottom of the growing object, then aftereach irradiation step the object under construction must be separatedfrom the bottom plate in the fabrication well. An early example of sucha technique is given in Hull, U.S. Pat. No. 5,236,637, at FIG. 4, wherethe polymerizable liquid is floated on top of a non-wetting immiscibleliquid layer. Such techniques have not, however, been commercialized,and dramatically different techniques for “bottom up” fabrication havebeen implemented instead. For example, in U.S. Pat. No. 7,438,846, anelastic separation layer is used to achieve “non-destructive” separationof solidified material at the bottom construction plane. Otherapproaches, such as the B9Creator™ 3-dimensional printer marketed byB9Creations of Deadwood, S. Dak., USA, employ a sliding build plate.See, e.g., M. Joyce, US Patent App. 2013/0292862 and Y. Chen et al., USPatent App. 2013/0295212 (both Nov. 7, 2013); see also Y. Pan et al., J.Manufacturing Sci. and Eng. 134, 051011-1 (October 2012). Suchapproaches introduce a mechanical step that may complicate theapparatus, slow the method, and/or potentially distort the end product.Accordingly, there is a need for alternate methods and apparatus forthree-dimensional fabrication that can obviate the need for mechanicalseparation steps in “bottom-up” fabrication.

SUMMARY OF THE INVENTION

A first aspect of the invention is a method of forming athree-dimensional object, comprising the steps of:

-   -   providing a carrier and a pool of immiscible liquid, the pool        having a liquid build surface, the carrier and the liquid build        surface defining a build region therebetween;    -   filling the build region with a polymerizable liquid, wherein        the immiscible liquid is immiscible with the polymerizable        liquid (e.g. wherein the immiscible liquid has a density greater        than the polymerizable liquid); and    -   irradiating (e.g., with patterned irradiation, where the pattern        changes over time) the build region through at least a portion        of the liquid to form a solid polymer from the polymerizable        liquid while (optionally but preferably) concurrently advancing        the carrier away from the liquid build surface to form the        three-dimensional object comprised of the solid polymer from the        polymerizable liquid (or in other embodiments, carrying out        irradiating advancing in separate, step-wise fashion, so that        the three-dimensional object is constructed in a layer-by-layer        fashion).

In some embodiments, the method comprises, also concurrently with theirradiating step, continuously maintaining a gradient of polymerizationzone (sometimes referred to as an “active surface” as discussed below)between the liquid build surface and the solid polymer and in contactwith each thereof, the gradient of polymerization zone comprising thepolymerizable liquid in partially cured form. In other embodiments, thethree-dimensional object may be formed in a layer-by-layer manner. Thefirst is in some embodiments referred to as “CLIP” for “continuousliquid interface production,” “continuous liquid interphase printing,”or other variants thereof (See, e.g., J. Desimone, A. Ermoshkin, N.Ermoshkin, and E. Samulski, Continuous Liquid Interphase Printing, PCTApplication Pub. No. WO 2014/126837 (21 Aug. 2014); see also J.Tumbleston et al., Continuous liquid interface production of 3d objects,Science 347, 1349-1352 (published online 16 Mar. 2015)).

A further aspect of the invention is a liquid system useful for forminga three-dimensional object, comprising, consisting of or consistingessentially of:

-   -   (a) from 1, 2 or 5 percent to 90, 95 or 99.9 percent by weight        of a polymerizable liquid from which a three-dimensional object        may be formed; and    -   (b) from 0.1, 5, or 10 percent to 95, 97 or 99 percent by weight        of an immiscible liquid, wherein the immiscible liquid: (i) has        a density greater than the polymerizable liquid, (ii) is        immiscible with the polymerizable liquid, and (iii) is wettable        with the polymerizable liquid. Ingredients such as surfactants,        wetting agents, viscosity-enhancing agents, pigments, and        particles may optionally be included in either or both of the        polymerizable liquid or immiscible liquid, as discussed further        below.

In some embodiments, the irradiating step is carried out underconditions in which the immiscible liquid is wettable with orsufficiently wettable with the polymerizable liquid (e.g., such that acontinuous film or layer of the polymerizable liquid spreads on thesurface of the immiscible liquid; and/or, under conditions in which thecontact angle of the polymerizable liquid on the immiscible liquid isnot more than 60, 90, 120, or 150 degrees).

In some embodiments, the immiscible liquid is a single phase solution.

In some embodiments, the immiscible liquid is an aqueous liquid.

In some embodiments, the immiscible liquid has a density of at least1.13, 1.15, or 1.2 grams per cubic centimeter.

In some embodiments, the irradiating step is carried out underconditions in which the viscosity of the polymerizable liquid is notgreater than the viscosity of the immiscible liquid.

In some embodiments, the polymerizable liquid comprises a free radicalpolymerizable liquid or an acid catalyzed polymerizable liquid.

In some embodiments, either or both of the immiscible liquid and thepolymerizable liquid further comprises a wetting agent (e.g., asurfactant).

In some embodiments, the immiscible liquid further comprises adensity-enhancing agent (e.g., a salt).

In some embodiments, the immiscible liquid further comprises aviscosity-enhancing agent (e.g., sugars, polyols, water solublepolymers, etc.).

In some embodiments, the method further comprises the step of coolingthe pool (e.g., to dissipate heat of polymerization created byirradiating polymerizable liquid in the build region, and/or stabilizethe pool). In some embodiments, the pool is at least partially frozen.

In some embodiments, the method further comprises the step of heatingthe pool (e.g., to reduce the viscosity of the polymerizable liquid, forexample to enhance the rate or speed of forming the three dimensionalobject).

In some embodiments of the method, the filling step is carried out byforcing the polymerizable liquid into the build region under pressure(e.g., to enhance the rate or speed of forming the three dimensionalobject).

Continuous processes for producing a three-dimensional object aresuggested at some length with respect to “top down” techniques in U.S.Pat. No. 7,892,474, but this reference does not explain how they may beimplemented in “bottom up” systems in a manner non-destructive to thearticle being produced.

Non-limiting examples and specific embodiments of the present inventionare explained in greater detail in the drawings herein and thespecification set forth below. The disclosure of all United StatesPatent references cited herein are to be incorporated herein byreference in their entirety.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of one embodiment of a method of thepresent invention.

FIG. 2 is a side schematic view of one embodiment of an apparatus usefulfor carrying out the method of the present invention.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention is now described more fully hereinafter withreference to the accompanying drawings, in which embodiments of theinvention are shown. This invention may, however, be embodied in manydifferent forms and should not be construed as limited to theembodiments set forth herein; rather these embodiments are provided sothat this disclosure will be thorough and complete and will fully conveythe scope of the invention to those skilled in the art.

Like numbers refer to like elements throughout. In the figures, thethickness of certain lines, layers, components, elements or features maybe exaggerated for clarity. Where used, broken lines illustrate optionalfeatures or operations unless specified otherwise.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the invention. Asused herein, the singular forms “a,” “an” and “the” are intended toinclude plural forms as well, unless the context clearly indicatesotherwise. It will be further understood that the terms “comprises” or“comprising,” when used in this specification, specify the presence ofstated features, integers, steps, operations, elements components and/orgroups or combinations thereof, but do not preclude the presence oraddition of one or more other features, integers, steps, operations,elements, components and/or groups or combinations thereof.

As used herein, the term “and/or” includes any and all possiblecombinations or one or more of the associated listed items, as well asthe lack of combinations when interpreted in the alternative (“or”).

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this invention belongs. It will befurther understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the specification andclaims and should not be interpreted in an idealized or overly formalsense unless expressly so defined herein. Well-known functions orconstructions may not be described in detail for brevity and/or clarity.

It will be understood that when an element is referred to as being “on,”“attached” to, “connected” to, “coupled” with, “contacting,” etc.,another element, it can be directly on, attached to, connected to,coupled with and/or contacting the other element or intervening elementscan also be present. In contrast, when an element is referred to asbeing, for example, “directly on,” “directly attached” to, “directlyconnected” to, “directly coupled” with or “directly contacting” anotherelement, there are no intervening elements present. It will also beappreciated by those of skill in the art that references to a structureor feature that is disposed “adjacent” another feature can have portionsthat overlap or underlie the adjacent feature.

Spatially relative terms, such as “under,” “below,” “lower,” “over,”“upper” and the like, may be used herein for ease of description todescribe an element's or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is inverted, elements described as “under” or “beneath” otherelements or features would then be oriented “over” the other elements orfeatures. Thus the exemplary term “under” can encompass both anorientation of over and under. The device may otherwise be oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly. Similarly, the terms“upwardly,” “downwardly,” “vertical,” “horizontal” and the like are usedherein for the purpose of explanation only, unless specificallyindicated otherwise.

It will be understood that, although the terms first, second, etc., maybe used herein to describe various elements, components, regions, layersand/or sections, these elements, components, regions, layers and/orsections should not be limited by these terms. Rather, these terms areonly used to distinguish one element, component, region, layer and/orsection, from another element, component, region, layer and/or section.Thus, a first element, component, region, layer or section discussedherein could be termed a second element, component, region, layer orsection without departing from the teachings of the present invention.The sequence of operations (or steps) is not limited to the orderpresented in the claims or figures unless specifically indicatedotherwise.

1. Polymerizable Liquids.

Any suitable polymerizable liquid can be used to enable the presentinvention. The liquid (sometimes also referred to as “liquid resin”“ink,” or simply “resin” herein) can include a monomer, particularlyphotopolymerizable and/or free radical polymerizable monomers, and asuitable initiator such as a free radical initiator, and combinationsthereof. Examples include, but are not limited to, acrylics,methacrylics, acrylamides, styrenics, olefins, halogenated olefins,cyclic alkenes, maleic anhydride, alkenes, alkynes, carbon monoxide,functionalized oligomers, multifunctional cure site monomers,functionalized PEGs, etc., including combinations thereof. Examples ofliquid resins, monomers and initiators include but are not limited tothose set forth in U.S. Pat. Nos. 8,232,043; 8,119,214; 7,935,476;7,767,728; 7,649,029; WO 2012129968 A1; CN 102715751 A; JP 2012210408 A.

Acid Catalyzed Polymerizable Liquids.

While in some embodiments as noted above the polymerizable liquidcomprises a free radical polymerizable liquid (in which case aninhibitor may be oxygen as described below), in other embodiments thepolymerizable liquid comprises an acid catalyzed, or cationicallypolymerized, polymerizable liquid. In such embodiments the polymerizableliquid comprises monomers contain groups suitable for acid catalysis,such as epoxide groups, vinyl ether groups, etc. Thus suitable monomersinclude olefins such as methoxyethene, 4-methoxystyrene, styrene,2-methylprop-1-ene, 1,3-butadiene, etc.; heterocycloic monomers(including lactones, lactams, and cyclic amines) such as oxirane,thietane, tetrahydrofuran, oxazoline, 1,3, dioxepane, oxetan-2-one,etc., and combinations thereof. A suitable (generally ionic ornon-ionic) photoacid generator (PAG) is included in the acid catalyzedpolymerizable liquid, examples of which include, but are not limited toonium salts, sulfonium and iodonium salts, etc., such as diphenyl iodidehexafluorophosphate, diphenyl iodide hexafluoroarsenate, diphenyl iodidehexafluoroantimonate, diphenyl p-methoxyphenyl triflate, diphenylp-toluenyl triflate, diphenyl p-isobutylphenyl triflate, diphenylp-tert-butylphenyl triflate, triphenylsulfonium hexafluororphosphate,triphenylsulfonium hexafluoroarsenate, triphenylsulfoniumhexafluoroantimonate, triphenylsulfonium triflate,dibutylnaphthylsulfonium triflate, etc., including mixtures thereof.See, e.g., U.S. Pat. Nos. 7,824,839; 7,550,246; 7,534,844; 6,692,891;5,374,500; and 5,017,461; see also Photoacid Generator Selection Guidefor the electronics industry and energy curable coatings (BASF 2010).

Hydrogels.

In some embodiments suitable resins includes photocurable hydrogels likepoly(ethylene glycols) (PEG) and gelatins. PEG hydrogels have been usedto deliver a variety of biologicals, including Growth factors; however,a great challenge facing PEG hydrogels crosslinked by chain growthpolymerizations is the potential for irreversible protein damage.Conditions to maximize release of the biologicals from photopolymerizedPEG diacrylate hydrogels can be enhanced by inclusion of affinitybinding peptide sequences in the monomer resin solutions, prior tophotopolymerization allowing sustained delivery. Gelatin is a biopolymerfrequently used in food, cosmetic, pharmaceutical and photographicindustries. It is obtained by thermal denaturation or chemical andphysical degradation of collagen. There are three kinds of gelatin,including those found in animals, fish and humans. Gelatin from the skinof cold water fish is considered safe to use in pharmaceuticalapplications. UV or visible light can be used to crosslink appropriatelymodified gelatin. Methods for crosslinking gelatin include curederivatives from dyes such as Rose Bengal.

Photocurable Silicone Resins.

A suitable resin includes photocurable silicones. UV cure siliconerubber, such as Siliopren™ UV Cure Silicone Rubber can be used as canLOCTITE™ Cure Silicone adhesives sealants. Applications include opticalinstruments, medical and surgical equipment, exterior lighting andenclosures, electrical connectors/sensors, fiber optics and gaskets.

Biodegradable Resins.

Biodegradable resins are particularly important for implantable devicesto deliver drugs or for temporary performance applications, likebiodegradable screws and stents (U.S. Pat. Nos. 7,919,162; 6,932,930).Biodegradable copolymers of lactic acid and glycolic acid (PLGA) can bedissolved in PEG dimethacrylate to yield a transparent resin suitablefor use. Polycaprolactone and PLGA oligomers can be functionalized withacrylic or methacrylic groups to allow them to be effective resins foruse.

Photocurable Polyurethanes.

A particularly useful resin is photocurable polyurethanes. Aphotopolymerizable polyurethane composition comprising (1) apolyurethane based on an aliphatic diisocyanate, poly(hexamethyleneisophthalate glycol) and, optionally, 1,4-butanediol; (2) apolyfunctional acrylic ester; (3) a photoinitiator; and (4) ananti-oxidant, can be formulated so that it provides a hard,abrasion-resistant, and stain-resistant material (U.S. Pat. No.4,337,130). Photocurable thermoplastic polyurethane elastomersincorporate photoreactive diacetylene diols as chain extenders.

High Performance Resins.

In some embodiments, high performance resins are used. Such highperformance resins may sometimes require the use of heating to meltand/or reduce the viscosity thereof, as noted above and discussedfurther below. Examples of such resins include, but are not limited to,resins for those materials sometimes referred to as liquid crystallinepolymers of esters, ester-imide, and ester-amide oligomers, as describedin U.S. Pat. Nos. 7,507,784; 6,939,940. Since such resins are sometimesemployed as high-temperature then moset resins, in the present inventionthey further comprise a suitable photoinitiator such as benzophenone,anthraquinone, and fluoroenone initiators (including derivativesthereof), to initiate cross-linking on irradiation, as discussed furtherbelow.

Additional Example Resins.

Particularly useful resins for dental applications include EnvisionTEC'sClear Guide, EnvisionTEC's E-Denstone Material. Particularly usefulresins for hearing aid industries include EnvisionTEC's e-Shell 300Series of resins. Particularly useful resins include EnvisionTEC's HTM1401V High Temperature Mold Material for use directly with vulcanizedrubber in molding/casting applications. A particularly useful materialfor making tough and stiff parts includes EnvisionTEC's RC31 resin. Aparticulary useful resin for investment casting applications includesEnvisionTEC's Easy Cast EC500.

Sol-Gel Polymerizable Liquids.

In some embodiments, the polymerizable liquid may comprise a solsolution, or acid-catalyzed sol. Such solutions generally comprise anmetal alkoxide including silicon and titanium alkoxides such as silicontetraethoxide (tetraethyl ortholsilicate; TEOS) in a suitable solvent.Products with a range of different properties can be so generated, fromrubbery materials (e.g., using silane-terminated silicone rubberoligomers) to very rigid materials (glass using only TEOS), andproperties in between using TEOS combinations with varioussilane-terminated oligomers. Additional ingredients such as dyes anddopants may be included in the sol solution as as is known in the art,and post-polymerization firing steps may be include as is known in theart. see, e.g., U.S. Pat. Nos. 4,765,818; 7,709,597; 7,108,947;8,242,299; 8,147,918; 7,368,514; etc. Where the sol solution is acidpolymerized, suitable inhibitors include bases such as ammonia asdiscussed further below.

Additional Resin Ingredients.

The liquid resin or polymerizable material can have solid particlessuspended or dispersed therein. Any suitable solid particle can be used,depending upon the end product being fabricated. The particles can bemetallic, organic/polymeric, inorganic, or composites or mixturesthereof. The particles can be nonconductive, semi-conductive, orconductive (including metallic and non-metallic or polymer conductors);and the particles can be magnetic, ferromagnetic, paramagnetic, ornonmagnetic. The particles can be of any suitable shape, includingspherical, elliptical, cylindrical, etc. The particles can comprise anactive agent or detectable compound as described below, though these mayalso be provided dissolved solubilized in the liquid resin as alsodiscussed below. For example, magnetic or paramagnetic particles ornanoparticles can be employed.

The liquid resin can have additional ingredients solubilized therein,including pigments, dyes, active compounds or pharmaceutical compounds,detectable compounds (e.g., fluorescent, phosphorescent, radioactive),etc., again depending upon the particular purpose of the product beingfabricated. Examples of such additional ingredients include, but are notlimited to, proteins, peptides, nucleic acids (DNA, RNA) such as siRNA,sugars, small organic compounds (drugs and drug-like compounds), etc.,including combinations thereof.

Inhibitors of Polymerization.

In some embodiments, the immiscible liquid may have a polymerizationinhibitor dissolved or solubilized therein. Such inhibitors may be usedto establish a “dead zone” within the gradient of polymerization closestto the immiscible liquid, where polymerization is completely inhibited,with polymerization progressively more complete in the regions of thegradient furthest from the immiscible liquid. Inhibitors orpolymerization inhibitors for use in the present invention may be in theform of a liquid or a gas. In some embodiments, gas inhibitors arepreferred. The specific inhibitor will depend upon the monomer beingpolymerized and the polymerization reaction. For free radicalpolymerization monomers, the inhibitor can conveniently be oxygen, whichcan be provided in the form of a gas such as air, a gas enriched inoxygen (optionally but in some embodiments preferably containingadditional inert gases to reduce combustibility thereof), or in someembodiments pure oxygen gas. In alternate embodiments, such as where themonomer is polymerized by photoacid generator initiator, the inhibitorcan be a base such as ammonia, trace amines (e.g. methyl amine, ethylamine, di and trialkyl amines such as dimethyl amine, diethyl amine,trimethyl amine, triethyl amine, etc.), or carbon dioxide, includingmixtures or combinations thereof.

In addition to or in alternative to the foregoing, the polymerizationinhibitor (e.g., for inhibiting free-radically polymerized materials)may be an organic compound, examples of which include, but are notlimited to, monomethyl ether hydroquinone,bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate,1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate,aluminum-nitrosophenylhydroxylamine, butylated hydroxytoluene,phenothiazine, hydroquinone, methoxyquinone, 1,4-phenylenediamine,p-anisole, 2,6-di-tert-butyl-4-methylphenol (BHT), methylhydroquinone,ethylhydroquinone, methoxyhydroquinone, ethoxyhydroquinone,monomethylether hydroquinone, propylhydroquinone, propoxyhydroquinone,tert-butylhydroquinone, n-butylhydroquinone, derivatives thereof, andcombinations thereof. See, e.g., U.S. Pat. Nos. 8,389,593 and 8,017,193.

Polymerizable Liquids Carrying Live Cells.

In some embodiments, the polymerizable liquid may carry live cells as“particles” therein. Such polymerizable liquids are generally aqueous,and may be oxygenated, and may be considered as “emulsions” where thelive cells are the discrete phase. Suitable live cells may be plantcells (e.g., monocot, dicot), animal cells (e.g., mammalian, avian,amphibian, reptile cells), microbial cells (e.g., prokaryote, eukaryote,protozoal, etc.), etc. The cells may be of differentiated cells from orcorresponding to any type of tissue (e.g., blood, cartilage, bone,muscle, endocrine gland, exocrine gland, epithelial, endothelial, etc.),or may be undifferentiated cells such as stem cells or progenitor cells.In such embodiments the polymerizable liquid can be one that forms ahydrogel, including but not limited to those described in U.S. Pat. Nos.7,651,683; 7,651,682; 7,556,490; 6,602,975; 5,836,313; etc.

2. Apparatus.

The methods of the present invention can be implemented with a varietyof different apparatus. In the simplest embodiment, an apparatus asdescribed in U.S. Pat. No. 5,236,637 to Hull at FIG. 4 therein may beused. More preferably, however, an apparatus as shown in FIG. 2 hereinis employed. In brief overview, such an apparatus includes a vessel forcontaining an immiscible liquid, with a polymerizable liquid floating ontop of the immiscible liquid (the density of the polymerizable liquidbeing less than the density of the immiscible liquid). A window (e.g.,glass) is positioned at the bottom of the vessel, through which anirradiation source may irradiate the build region. A carrier ispositioned over the vessel which gradually and progressively advancesthe growing three-dimensional object up and out of the polymerizableliquid. At least one temperature sensor or thermocouple is positioned inthe vessel, along with at least one heater and/or cooler (e.g., aPeltier cooler), all positioned to contact the immiscible liquid. Acontroller (e.g., a computer with appropriate interface and program) maybe provided (not shown), which operates the carrier, heater, and cooler,e.g., responsive to data such as current temperature of the immiscibleliquid as determined by the temperature sensor. Additional andalternative features of the apparatus, and the operation thereof, arediscussed further below.

Numerous variations on the apparatus described in FIG. 2 above can beemployed. For example, pool depth in the apparatus may be varied fromthin or shallow to deep, depending on factors such as the composition ofthe immiscible liquid, the structure of the apparatus, etc. For example,the pool depth may be desired to be sufficiently thick that the heat ofpolymerization at the reaction zone can be transferred into the pool ofimmiscible liquid. In some embodiments, the pool may have a depth of atleast 1, 5 or 10 microns, up to 1, 5, or 10 millimeters, or more. Inother embodiments, the pool may have a depth of at least 1, 5, or 10millimeters, up to 10, 50 or 100 millimeters, or more.

While in the illustrated embodiments the pool is shown as a static orstationary pool, in other embodiments circulation of immiscible liquidmay be provided through the pool, for example to cool the pool, orrefresh oxygen content therein (e.g., of fluorinated fluids).

Irradiation may be through a window positioned at the bottom of the poolas illustrated above, through the side of the pool (e.g., aided by amirror or mirror assembly within the pool), may be achieved with a lightsource positioned entirely within the pool, may be achieved with a fiberoptic or light pipe having a terminus within the pool, etc.

Any suitable radiation source (or combination of sources) can be used inthe apparatus, depending upon the particular resin employed, includingelectron beam and ionizing radiation sources. In a preferred embodimentthe radiation source is an actinic radiation source, such as one or morelight sources, and in particular one or more ultraviolet light sources.Any suitable light source can be used, such as incandescent lights,fluorescent lights, phosphorescent or luminescent lights, a laser,light-emitting diode, etc., including arrays thereof. The light sourcepreferably includes a pattern-forming element operatively associatedwith a controller, as noted above. In some embodiments, the light sourceor pattern forming element comprises a digital (or deformable)micromirror device (DMD) with digital light processing (DLP), a spatialmodulator (SLM), or a microelectromechanical system (MEMS) mirror array,a mask (aka a reticle), a silhouette, or a combination thereof. See,U.S. Pat. No. 7,902,526. Preferably the light source comprises a spatiallight modulation array such as a liquid crystal light valve array ormicromirror array or DMD (e.g., with an operatively associated digitallight processor, typically in turn under the control of a suitablecontroller), configured to carry out exposure or irradiation of thepolymerizable liquid without a mask, e.g., by maskless photolithography.See, e.g., U.S. Pat. Nos. 6,312,134; 6,248,509; 6,238,852; and5,691,541.

While in some embodiments the carrier is mounted on an elevator toadvance up and away from a stationary build plate, on other embodimentsthe converse arrangement may be used: That is, the carrier may be fixedand the build plate lowered to thereby advance the carrier awaytherefrom. Numerous different mechanical configurations will be apparentto those skilled in the art to achieve the same result, in all of whichthe build plate is “stationary” in the sense that no lateral (X or Y)movement is required to replenish the inhibitor thereon, or no elasticbuild plate that must be stretched and then rebound (with associatedover-advance, and back-up of, the carrier) need be employed.

Depending on the choice of material from which the carrier isfabricated, and the choice of polymer or resin from which the article ismade, adhesion of the article to the carrier may sometimes beinsufficient to retain the article on the carrier through to completionof the finished article or “build.” For example, an aluminum carrier mayhave lower adhesion than a poly(vinyl chloride) (or “PVC”) carrier.Hence one solution is to employ a carrier comprising a PVC on thesurface to which the article being fabricated is polymerized. If thispromotes too great an adhesion to conveniently separate the finishedpart from the carrier, then any of a variety of techniques can be usedto further secure the article to a less adhesive carrier, including butnot limited to the application of adhesive tape such as “Greener MaskingTape for Basic Painting #2025 High adhesion” to further secure thearticle to the carrier during fabrication.

Soluble Sacrificial Layers.

In some embodiments, a soluble sacrificial layer or release layer may beestablished between the carrier and the three-dimensional object, sothat that sacrificial layer may be subsequently solubilized toconveniently release the three-dimensional object from the carrier oncefabrication is complete. Any suitable sacrificial layer, such as anadhesive, that may be coated or otherwise provided on the carrier may beemployed, and any suitable solvent (e.g., polar and non-polar organicsolvents, aqueous solvents, etc.) to solubilize the sacrificial releaselayer may be employed, though the sacrificial layer and itscorresponding solvent should be chosen so that the particular materialfrom which the three-dimensional object is formed is not itself undulyattacked or solubilized by that solvent. The sacrificial layer may beapplied to the carrier by any suitable technique, such as spraying, dipcoating, painting, etc. Examples of suitable materials for the solublesacrificial release layer (and non-limiting examples of correspondingsolvents) include but are not limited to: cyanoacrylate adhesive(acetone solvent); poly(vinylpyrrolidone) (water and/or isopropylalcohol solvent); lacquers (acetone solvent); polyvinyl alcohol,polyacrylic acid, poly(methacrylic acid), polyacrylamide, polyalkyleneoxides such as poly(ethylene oxide), sugars and saccharides such assucrose and dextran (all water or aqueous solvents); etc. Lower surfaceenergy solvents are in some embodiments particularly preferred.

In some embodiments of the invention, the actuator/drive and/orassociated controller are configured to only advance the carrier awayfrom the build region (e.g., is unidirectional), as discussed furtherbelow.

In some embodiments of the invention, the actuator/drive and/orassociated controller are configured as a continuous drive (as opposedto a step-wise drive), as also discussed below.

3. Immiscible Liquids and Liquid Systems.

Immiscible Liquids.

While Hull et al. suggests “non-wetting” liquids as the immiscibleliquid, this is problematic, particularly for continuous processes, as a“non-wetting” reaction liquid would not easily spread over theimmiscible liquid surface as the growing three-dimensional product or“build” is moved upward as polymerization proceeds. Additionally aslarge parts (x and y direction) are made the ability of thepolymerizable liquid to flow or “spread” over the immiscible liquid (andpreferably form a continuous film or layer on top of the immiscibleliquid, and not form beads, droplets, or other discontinuous regions) isparticularly important. Hence it is preferable that the immiscibleliquid is sufficiently “wettable” with the polymerizable liquid so thatthe polymerizable liquid can enter, or flow into, the polymerizationzone as the polymerized liquid, or growing build object, is movedvertically.

The property of “wetting”, “wettability” or “wettable” is generallydefined with reference to the “contact angle” formed when one liquid isplaced on top of another (liquid or solid; in the present case liquid)surface. A contact angle of zero degrees indicates perfectly wettingproperties; a contact angle between zero and ninety degrees generallyindicates high wetting properties; a contact angle between ninety andone hundred and eighty degrees generally indicates low wettingproperties; a contact angle of 180 degrees indicates perfectlynon-wetting properties. It is not required that perfect wetting beachieved, and some lower wettability combinations may be satisfactory insome circumstances (e.g., where a deep layer of polymerizable liquid isdeposited on top of a sufficiently deep pool of immiscible liquid), butit is generally preferred that the contact angle between thepolymerizable liquid and immiscible liquid, during the irradiatingsteps, be less than 150, 120, or 90 degrees be achieved. If suchwettability is not inherently achieved by the particular combination ofpolymerizable liquid and immiscible liquid, wettability between the twoliquids can be increased by the inclusion of one or more wetting agentsin either or both of the liquids, as discussed further below.

It should be noted that contact angles are generally defined forsolid-liquid interfaces with limited references to liquid-liquidinterfaces. Thus wetting is usually defined for a combination of a solidand a liquid. Wetting can be defined for immiscible liquid mixturesusing the spreading coefficient. For the case of liquid B spreading overliquid A the relevant equation is:S_(B/A)=γ_(A)−γ_(AB)where:

S is the spreading coefficient,

γ_(A) is the surface tension of liquid A,

γ_(B) is the surface tension of liquid B and

γ_(AB) is the interfacial tension between A and B.

If the spreading coefficient is greater than zero, liquid B willspontaneously spread over liquid A. Note the value of the reversespreading coefficient S_(A/B) will be different than S_(B/A).Hydrocarbons such as benzene, isopentane, hexane have positive spreadingcoefficients over water initially but under equilibrium conditionsnegative values are observed. This results in a lens of a large dropletof the hydrocarbon on the water surface. As more hydrocarbon is added,this lens will spread out a form a continuous layer over water. Thespreading of oil from an oil spill into water to form an oil “slick” hasbeen widely studied. In this case “spreading” does not mean that thespreading coefficient is positive. The “lens” can be employed todetermine the contact angle. From the tangent line to the water surfaceat the point of contact of the lens (where water, lens and air exist)and the tangent line of the oil surface also at the point of contact,the contact angle can be defined from the intersection of these tangentlines. The contact angle is defined as the angle between these lineswhich comprises the liquid lens space. If the contact angle is too largeand the spreading coefficient is too negative, the flow of liquid B (inthis case the polymerizable liquid) into a narrow gap over liquid Aresulting from vertical displacement of the part will be more difficult.For a perfectly or highly non-wettable immiscible liquid surface,dewetting may occur in the polymerization zone as the part is movedvertically creating voids. Thus for the purposes of this invention, somelevel of wetting is required. Also for the purposes of this inventionthe terms “spreading” and “spreads” does not mean the spreadingcoefficient is positive but rather that the polymerizable liquid has thecapability of flowing or spreading over the surface of the immiscibleliquid in the zone of polymerization to replenish the polymerizableliquid region.

Density Enhancing.

Aqueous liquids are preferred for the immiscible liquid in manyembodiments. However, as water has a density of 1.0 g/cm³, it does nothave a density high enough to be more dense than many potentialpolymerizable liquids. A denser form of water known in the art as heavywater (deuterium oxide; D₂O) only has a density of about 1.11 g/cm³ andmay not be sufficient for many desirable polymerizable liquids. Hence,to increase the density of water, one or more salts can be added to theaqueous liquid to form salt solutions thereof. These solutionspreferably maintain transparency up to their solubility limit and bereasonably transparent to UV at 365 nm (a preferred UV wavelength) as athin film layer. As examples, water with 25 wt % NaCl has a density of1.193 g/cm³; Dead Sea water has a density is 1.240 g/cm³. The density ofvarious salts that may be used, singly or in any combination thereof,and their solubility limit in water is listed in the Table below:

Solubility limit in water Salt Salt density (anhydrous) g/cc around roomtemperature NaCl 2.165 35.9 g/100 ml NaBr 3.21 90.5 g/100 ml KBr 2.7467.8 g/100 ml MgBr₂ 3.72  102 g/100 ml MgCl₂ 2.32 54.3 g/100 ml Sodiumacetate 1.528 46.4 g/100 ml Sodium nitrate 2.257 91.2 g/100 ml CaBr₂3.353  143 g/100 ml CaCl₂ 2.15 74.5 g/100 ml Na₂CO₃ 2.54 21.5 g/100 mlNH₄Br 2.429 78.3 g/100 ml LiBr 3.464 166.7 g/100 ml 

Viscosity.

Soluble organic compounds can also be added to aqueous (and nonaqueous)immiscible liquids to increase the density, increase the viscosity(syrup-like), and modify the wetting characteristics to reactionsystems. These mixtures can be modified with salt as discussed above toincrease the density and optionally water soluble polymers (discussedbelow) to further increase the viscosity of the immiscible liquid.

Organic Solubility in water around compound Density (anhydrous) g/ccroom temperature glycerol 1.261 glucose 1.54 90.0 g/100 ml  fructose1.694 sucrose 1.587 200 g/100 ml maltose 1.54 108 g/100 ml Ethyleneglycol 1.1132 soluble Triethylene glycol 1.1255 soluble Diethyleneglycol 1.118 soluble Glutaric acid 1.429 >50%

In some embodiments viscosity mismatch between the immiscible liquid andthe polymerizable liquid may be a problem. In this case, water solublepolymers can be added to water (and the water solutions discussed above)to increase the viscosity. Examples of suitable polymers include but arenot limited to poly(ethylene oxide), poly (vinyl pyrrolidone),poly(acrylic acid), poly(methacrylic acid) poly(ethyl oxazoline),poly(ethylene imine), poly(vinyl amine), carboxy methyl cellulose, andthe like. A specific case where extremely high viscosities may bedesired would involve a hydrogel layer on glass. In this case a lightlycrosslinked water soluble polymer (like poly(acrylic acid)) can beattached to glass and saturated with water. Indeed, in some embodimentsthis condition may not require a higher density than the reaction systemand may allow a stable layer that resists adhesion of the polymerizedreaction system, allowing easy removal of the three dimensional objectfrom the apparatus.

Wetting Agents.

Modification of the wetting properties can be accomplished by additionof a surfactant to the immiscible liquid and/or the polymerizableliquid. In the case of addition of a surfactant to the liquid layercomprised of water and water solutions as discussed above a litany ofpotential surfactants can be considered. A surfactant in this caselowers the interfacial tension between the two layers. These includenonionic, anionic and cationic surfactants. Examples include, but notlimited to: sodium stearate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, dioctadecyldimethylammonium chloride, octaethyleneglycol monododecyl ether, poly(propylene glycol)-poly(ethylene glycol)block copolymers, polyoxyethylene glycol octylphenol ethers,polyethoxylated tallow amines. Classes of these compounds include linearalkylbenzene sulfonates, fatty alcohol ethyoxylates, alkylphenolethoxylates, and lignin sulfonates. Silicone surfactants andfluorocarbon surfactants are also well known and can be used in thisprocess.

Reactive oligomers such as polyethylene glycol (“PEG”) diacrylates couldbe a problem with water as the liquid layer due to the affinity of thePEG oligomer for water. Polypropylene glycol (“PPG”) diacrylates andpoly(tetramethylene oxide) diacrylates do not have a affinity for waterand are also lower in density than the analogous PEG diacrylates.Reactive diluents such as styrene and acrylate monomers can be added todecrease the viscosity of the reaction system.

Nonaqueous Immiscible Liquids.

Although aqueous liquids are preferred for the immiscible liquid, insome embodiments preferred, nonaqueous liquid layers may be preferablefor specific reaction systems. Examples include higher densityhydrocarbon liquids such as ethylene glycol, diethylene glycol,triethylene glycol, glycerol, formamide, fluorocarbons andperfluorcarbon liquids such as Kytox (duPont) or Fomblin perfluorinatedpolyether oil. Low toxicity chlorinated aliphatic hydrocarbon liquidscould also be considered. Nonaqueous liquid salts (also referred to asionic liquids) can also be employed, examples of which include but arenot limited to 1-butyl-3,5-dimethylpyridinium bromide and1-butyl-3-methylimidazolium hexafluorophosphate.

Liquid Systems.

The polymerizable liquid and the immiscible liquid described above, canbe combined in situ in an apparatus to form a liquid system as describedherein, or can be packaged together in a suitable container, in anysuitable ratio or amount as described above, for storage, shipping, andsubsequent use.

4. Methods.

Once the polymerizable liquid and the immiscible liquid are suppliedtogether in a suitable apparatus and a sufficiently stable interfacebetween the two liquids is formed, fabrication of the three dimensionalobject may commence. As noted above, fabrication may be carried outlayer-by-layer or continuously, though continuous fabrication, achievedby establishing a gradient of polymerization as shown in FIG. 1 abovethrough adjustment of rate of advance, irradiation intensity, etc., ispreferred.

While the dead zone (when present) and the gradient of polymerizationzone do not have a strict boundary therebetween (in those locationswhere the two meet), the thickness of the gradient of polymerizationzone is in some embodiments at least as great as the thickness of thedead zone. Thus, in some embodiments, the dead zone has a thickness offrom 0.01, 0.1, 1, 2, or 10 microns up to 100, 200 or 400 microns, ormore, and/or said gradient of polymerization zone and said dead zonetogether have a thickness of from 1 or 2 microns up to 400, 600, or 1000microns, or more. Thus the gradient of polymerization zone (whethercontacting a dead zone, or an immiscible liquid) may be thick or thindepending on the particular process conditions at that time. Where thegradient of polymerization zone is thin, it may also be described as anactive surface on the bottom of the growing three-dimensional object,with which monomers can react and continue to form growing polymerchains therewith. In some embodiments, the gradient of polymerizationzone, or active surface, is maintained (while polymerizing stepscontinue) for a time of at least 5, 10, 15, 20 or 30 seconds, up to 5,10, 15 or 20 minutes or more, or until completion of thethree-dimensional product.

In some embodiments, the advancing step is carried out sequentially inuniform increments (e.g., of from 0.1 or 1 microns, up to 10 or 100microns, or more) for each step or increment. In some embodiments, theadvancing step is carried out sequentially in variable increments (e.g.,each increment ranging from 0.1 or 1 microns, up to 10 or 100 microns,or more) for each step or increment. The size of the increment, alongwith the rate of advancing, will depend in part upon factors such astemperature, pressure, structure of the article being produced (e.g.,size, density, complexity, configuration, etc.).

In other embodiments of the invention, the advancing step is carried outcontinuously, at a uniform or variable rate. Note that fabrication ofthe product may be continuous (as opposed to layer-by-layer) even whenthe advancing step is carried out in increments.

In some embodiments, the rate of advance (whether carried outsequentially or continuously) is from about 0.11, or 10 microns persecond, up to about to 100, 1,000, or 10,000 microns per second, againdepending again depending on factors such as temperature, pressure,structure of the article being produced, intensity of radiation, etc.

In some embodiments the filling step is carried out by forcing saidpolymerizable liquid into said build region under pressure. In such acase, the advancing step or steps may be carried out at a rate orcumulative or average rate of at least 0.1, 1, 10, 50, 100, 500 or 1000microns per second, or more. In general, the pressure may be whatever issufficient to increase the rate of said advancing step(s) at least 2, 4,6, 8 or 10 times as compared to the maximum rate of repetition of saidadvancing steps in the absence of said pressure. Where the pressure isprovided by enclosing an apparatus such as described above in a pressurevessel and carrying the process out in a pressurized atmosphere (e.g.,of air, air enriched with nitrogen, a blend of gases, etc.) a pressureof 10, 20, 30 or 40 pounds per square inch (PSI) up to, 200, 300, 400 or500 PSI or more, may be used. For fabrication of large irregular objectshigher pressures may be less preferred as compared to slower fabricationtimes due to the cost of a large high pressure vessel.

On the other hand, when smaller items are fabricated, or a rod or fiberis fabricated that can be removed or exited from the pressure vessel asit is produced through a port or orifice therein, then the size of thepressure vessel can be kept smaller relative to the size of the productbeing fabricated and higher pressures can (if desired) be more readilyutilized.

As noted above, the irradiating step is in some embodiments carried outwith patterned irradiation. The patterned irradiation may be a fixedpattern or may be a variable pattern created by a pattern generator(e.g., a DLP) as discussed above, depending upon the particular itembeing fabricated.

When the patterned irradiation is a variable pattern rather than apattern that is held constant over time, then each irradiating step maybe any suitable time or duration depending on factors such as theintensity of the irradiation, the presence or absence of dyes in thepolymerizable material, the rate of growth, etc. Thus in someembodiments each irradiating step can be from 0.001, 0.01, 0.1, 1 or 10microseconds, up to 1, 10, or 100 minutes, or more, in duration. Theinterval between each irradiating step is in some embodiments preferablyas brief as possible, e.g., from 0.001, 0.01, 0.1, or 1 microseconds upto 0.1, 1, or 10 seconds.

The methods and apparatus of the invention can include process steps andapparatus features to implement process control, including feedback andfeed-forward control, to, for example, enhance the speed and/orreliability of the method.

A controller for use in carrying out the present invention may beimplemented as hardware circuitry, software, or a combination thereof.In one embodiment, the controller is a general purpose computer thatruns software, operatively associated with monitors, drives, pumps, andother components through suitable interface hardware and/or software.Suitable software for the control of a three-dimensional printing orfabrication method and apparatus as described herein includes, but isnot limited to, the ReplicatorG open source 3d printing program,3DPrint™ controller software from 3D systems, Slic3r, Skeinforge,KISSlicer, RepetierHost, PrintRun, Cura, etc., including combinationsthereof.

Process parameters to directly or indirectly monitor, continuously orintermittently, during the process (e.g., during one, some or all ofsaid filling, irradiating and advancing steps) include, but are notlimited to, irradiation intensity, temperature of carrier, polymerizableliquid in the build zone, temperature of growing product, temperature ofimmiscible liquid, pressure, speed of advance, pressure, strain (e.g.,exerted on the carrier by the growing product being fabricated),thickness of release layer, etc.

Known parameters that may be used in feedback and/or feed-forwardcontrol systems include, but are not limited to, expected consumption ofpolymerizable liquid (e.g., from the known geometry or volume of thearticle being fabricated), degradation temperature of the polymer beingformed from the polymerizable liquid, etc.

Process conditions to directly or indirectly control, continuously orstep-wise, in response to a monitored parameter, and/or known parameters(e.g., during any or all of the process steps noted above), include, butare not limited to, rate of supply of polymerizable liquid, temperature,pressure, rate or speed of advance of carrier, intensity of irradiation,duration of irradiation (e.g. for each “slice”), etc.

For example, the temperature of the polymerizable liquid in the buildzone, or the temperature of the immiscible liquid, can be monitored,directly or indirectly with an appropriate thermocouple, non-contacttemperature sensor (e.g., an infrared temperature sensor), or othersuitable temperature sensor, to determine whether the temperatureexceeds the degradation temperature of the polymerized product. If so, aprocess parameter may be adjusted through a controller to reduce thetemperature in the build zone and/or of the immiscible liquid. Suitableprocess parameters for such adjustment may include: decreasingtemperature with a cooler, decreasing the rate of advance of thecarrier, decreasing intensity of the irradiation, decreasing duration ofradiation exposure, etc.

In addition, the intensity of the irradiation source (e.g., anultraviolet light source such as a mercury lamp) may be monitored with aphotodetector to detect a decrease of intensity from the irriadiationsource (e.g., through routine degredation thereof during use). Ifdetected, a process parameter may be adjusted through a controller toaccommodate the loss of intensity. Suitable process parameters for suchadjustment may include: increasing temperature with a heater, decreasingthe rate of advance of the carrier, increasing power to the lightsource, etc.

As another example, control of temperature and/or pressure to enhancefabrication time may be achieved with heaters and coolers (individually,or in combination with one another and separately responsive to acontroller), and/or with a pressure supply (e.g., pump, pressure vessel,valves and combinations thereof) and/or a pressure release mechanismsuch as a controllable valve (individually, or in combination with oneanother and separately responsive to a controller).

In some embodiments the controller is configured to maintain thegradient of polymerization zone/active surface described herein (see,e.g., FIG. 1) throughout the fabrication of some or all of the finalproduct. The specific configuration (e.g., times, rate or speed ofadvancing, radiation intensity, temperature, etc.) will depend uponfactors such as the nature of the specific polymerizable liquid and theproduct being created. Configuration to maintain the gradient ofpolymerization zone/active surface may be carried out empirically, byentering a set of process parameters or instructions previouslydetermined, or determined through a series of test runs or “trial anderror”; configuration may be provided through pre-determinedinstructions; configuration may be achieved by suitable monitoring andfeedback (as discussed above), combinations thereof, or in any othersuitable manner.

5. Fabrication Products.

Three-dimensional products produced by the methods and processes of thepresent invention may be final, finished or substantially finishedproducts, or may be intermediate products subject to furthermanufacturing steps such as surface treatment, laser cutting, electricdischarge machining, etc., is intended. Intermediate products includeproducts for which further additive manufacturing, in the same or adifferent apparatus, may be carried out). For example, a fault orcleavage line may be introduced deliberately into an ongoing “build” bydisrupting, and then reinstating, the gradient of polymerizationzone/active surface, to terminate one region of the finished product, orsimply because a particular region of the finished product or “build” isless fragile than others.

Numerous different products can be made by the methods and apparatus ofthe present invention, including both large-scale models or prototypes,small custom products, miniature or microminiature products or devices,etc. Examples include, but are not limited to, medical devices andimplantable medical devices such as stents, drug delivery depots,functional structures, microneedle arrays, fibers and rods such aswaveguides, micromechanical devices, microfluidic devices, etc.

Thus in some embodiments the product can have a height of from 0.1 or 1millimeters up to 10 or 100 millimeters, or more, and/or a maximum widthof from 0.1 or 1 millimeters up to 10 or 100 millimeters, or more. Inother embodiments, the product can have a height of from 10 or 100nanometers up to 10 or 100 microns, or more, and/or a maximum width offrom 10 or 100 nanometers up to 10 or 100 microns, or more. These areexamples only: Maximum size and width depends on the architecture of theparticular device and the resolution of the light source and can beadjusted depending upon the particular goal of the embodiment or articlebeing fabricated.

In some embodiments, the ratio of height to width of the product is atleast 2:1, 10:1, 50:1, or 100:1, or more, or a width to height ratio of1:1, 10:1, 50:1, or 100:1, or more.

In some embodiments, the product has at least one, or a plurality of,pores or channels formed therein, as discussed further below.

The processes described herein can produce products with a variety ofdifferent properties. Hence in some embodiments the products are rigid;in other embodiments the products are flexible or resilient. In someembodiments, the products are a solid; in other embodiments, theproducts are a gel such as a hydrogel. In some embodiments, the productshave a shape memory (that is, return substantially to a previous shapeafter being deformed, so long as they are not deformed to the point ofstructural failure). In some embodiments, the products are unitary (thatis, formed of a single polymerizable liquid); in some embodiments, theproducts are composites (that is, formed of two or more differentpolymerizable liquids). Particular properties will be determined byfactors such as the choice of polymerizable liquid(s) employed.

In some embodiments, the product or article made has at least oneoverhanging feature (or “overhang”), such as a bridging element betweentwo supporting bodies, or a cantilevered element projecting from onesubstantially vertical support body. Because of the unidirectional,continuous nature of some embodiments of the present processes, theproblem of fault or cleavage lines that form between layers when eachlayer is polymerized to substantial completion and a substantial timeinterval occurs before the next pattern is exposed, is substantiallyreduced. Hence, in some embodiments the methods are particularlyadvantageous in reducing, or eliminating, the number of supportstructures for such overhangs that are fabricated concurrently with thearticle.

The foregoing is illustrative of the present invention, and is not to beconstrued as limiting thereof. The invention is defined by the followingclaims, with equivalents of the claims to be included therein.

That which is claimed is:
 1. A method of forming a three-dimensional object, comprising the steps of: providing a carrier and a pool of immiscible liquid, said pool having a liquid build surface, said carrier and said liquid build surface defining a build region therebetween; filling said build region with a polymerizable liquid, wherein said immiscible liquid is immiscible with said polymerizable liquid, irradiating said build region through at least a portion of said pool of immiscible liquid to form a solid polymer from said polymerizable liquid and advancing said carrier away from said liquid build surface to form said three-dimensional object comprised of said solid polymer, wherein said irradiating step is carried out under conditions in which said immiscible liquid is wettable with said polymerizable liquid, and wherein said immiscible liquid further comprises a viscosity-enhancing agent.
 2. The method of claim 1, wherein said immiscible liquid is a single phase solution.
 3. The method of claim 1, wherein said immiscible liquid is an aqueous liquid.
 4. The method of claim 1, wherein said immiscible liquid has a density of at least 1.13 grams per cubic centimeter.
 5. The method of claim 1, wherein said irradiating step is carried out under conditions in which the viscosity of said polymerizable liquid is not greater than the viscosity of said immiscible liquid.
 6. The method of claim 1, wherein either or both of said immiscible liquid and said polymerizable liquid further comprises a wetting agent.
 7. The method of claim 1, further comprising the step of cooling said pool.
 8. The method of claim 7, wherein said pool is at least partially frozen.
 9. The method of claim 1, further comprising the step of heating said pool.
 10. The method of claim 1, wherein said pool is supported by a window, and said irradiating step is carried out by irradiating through said window.
 11. The method of claim 1, wherein the volume of said pool of immiscible liquid is the same during the formation of the three-dimensional object.
 12. The method of claim 1, wherein said viscosity-enhancing agent comprises glycerol, glucose, fructose, sucrose, maltose, ethylene glycol, triethylene glycol, diethylene glycol, or glutaric acid.
 13. A method of forming a three-dimensional object, comprising the steps of: providing a carrier and a pool of immiscible liquid, said pool having a liquid build surface, said carrier and said liquid build surface defining a build region therebetween; filling said build region with a polymerizable liquid, wherein said immiscible liquid is immiscible with said polymerizable liquid, irradiating said build region through at least a portion of said pool of immiscible liquid to form a solid polymer from said polymerizable liquid and advancing said carrier away from said liquid build surface to form said three-dimensional object comprised of said solid polymer, wherein said irradiating step is carried out under conditions in which said immiscible liquid is wettable with said polymerizable liquid, wherein said immiscible liquid further comprises a viscosity-enhancing agent, and wherein said viscosity-enhancing agent comprises a water soluble polymer.
 14. The method of claim 13, wherein the water soluble polymer comprises poly(ethylene oxide), poly(vinyl pyrrolidone), poly(acrylic acid), poly(methacrylic acid), poly(ethyl oxazoline), poly(ethylene imine), poly(vinyl amine), or carboxy methyl cellulose.
 15. The method of claim 13, wherein either or both of said immiscible liquid and said polymerizable liquid further comprises a wetting agent.
 16. The method of claim 15, wherein the wetting agent comprises a nonionic, anionic or cationic surfactant.
 17. The method of claim 13, wherein said pool is supported by a window, and said irradiating step is carried out by irradiating through said window.
 18. A method of forming a three-dimensional object, comprising the steps of: providing a carrier and a pool of immiscible liquid, said pool having a liquid build surface, and said carrier and said liquid build surface defining a build region therebetween; filling said build region with a polymerizable liquid, wherein said immiscible liquid is immiscible with said polymerizable liquid; and irradiating said build region through at least a portion of said pool of immiscible liquid to form a solid polymer from said polymerizable liquid and advancing said carrier away from said liquid build surface to form said three-dimensional object comprised of said solid polymer, wherein said immiscible liquid is circulated through said pool.
 19. The method of claim 18, further comprising cooling said pool with a cooler.
 20. The method of claim 18, wherein said immiscible liquid comprises a nonaqueous liquid.
 21. The method of claim 18, wherein said immiscible liquid comprises a fluorinated liquid.
 22. The method of claim 18, wherein said immiscible liquid comprises a nonaqueous fluorinated liquid.
 23. The method of claim 19, wherein said immiscible liquid comprises a nonaqueous fluorinated liquid.
 24. The method of claim 18, wherein said immiscible liquid comprises a fluorocarbon liquid or a perfluorcarbon liquid.
 25. The method of claim 18, wherein said immiscible liquid comprises a perfluorinated polyether oil.
 26. The method of claim 18, wherein said immiscible liquid further comprises a polymerization inhibitor.
 27. The method of claim 26, wherein the polymerization inhibitor comprises oxygen, and wherein oxygen content of the immiscible liquid is refreshed when the immiscible liquid is circulated through said pool.
 28. The method of claim 18, wherein said immiscible liquid further comprises a surfactant.
 29. The method of claim 18, wherein said pool is supported by a window, and said irradiating step is carried out by irradiating through said window.
 30. A method of forming a three-dimensional object, comprising the steps of: providing a carrier and a pool of immiscible liquid, said pool having a liquid build surface, and said carrier and said liquid build surface defining a build region therebetween; filling said build region with a polymerizable liquid, wherein said immiscible liquid is immiscible with said polymerizable liquid; and irradiating said build region through at least a portion of said pool of immiscible liquid to form a solid polymer from said polymerizable liquid and advancing said carrier away from said liquid build surface to form said three-dimensional object comprised of said solid polymer, wherein said immiscible liquid comprises a fluorinated liquid.
 31. The method of claim 30, wherein said immiscible liquid comprises a nonaqueous liquid.
 32. The method of claim 30, wherein said immiscible liquid comprises a fluorocarbon liquid or a perfluorcarbon liquid.
 33. The method of claim 30, wherein said immiscible liquid comprises a perfluorinated polyether oil.
 34. The method of claim 30, further comprising cooling said pool with a cooler.
 35. The method of claim 30, wherein said immiscible liquid further comprises a polymerization inhibitor.
 36. The method of claim 30, wherein said immiscible liquid further comprises a surfactant.
 37. The method of claim 30, wherein said pool is supported by a window, and said irradiating step is carried out by irradiating through said window.
 38. A method of forming a three-dimensional object, comprising the steps of: providing a carrier and a pool of immiscible liquid, said pool having a liquid build surface, and said carrier and said liquid build surface defining a build region therebetween; filling said build region with a polymerizable liquid, wherein said immiscible liquid is immiscible with said polymerizable liquid; and irradiating said build region through at least a portion of said pool of immiscible liquid to form a solid polymer from said polymerizable liquid and advancing said carrier away from said liquid build surface to form said three-dimensional object comprised of said solid polymer, wherein said irradiating step is carried out under conditions in which said immiscible liquid is wettable with said polymerizable liquid, and wherein said immiscible liquid further comprises a viscosity-enhancing agent.
 39. The method of claim 38, wherein said immiscible liquid is circulated through said pool.
 40. The method of claim 38, further comprising cooling said pool with a cooler.
 41. The method of claim 38, wherein either or both of said immiscible liquid and said polymerizable liquid further comprises a wetting agent.
 42. The method of claim 41, wherein the wetting agent comprises a nonionic, anionic or cationic surfactant.
 43. The method of claim 38, wherein said viscosity-enhancing agent comprises a water soluble polymer.
 44. The method of claim 38, wherein said viscosity-enhancing agent comprises glycerol, glucose, fructose, sucrose, maltose, ethylene glycol, triethylene glycol, diethylene glycol, or glutaric acid.
 45. The method of claim 38, wherein said immiscible liquid comprises a nonaqueous liquid.
 46. The method of claim 38, wherein said pool is supported by a window, and said irradiating step is carried out by irradiating through said window. 